EP2827986B1 - Métathèse d'oléfines avec des complexes catalytiques à base de ruthénium - Google Patents

Métathèse d'oléfines avec des complexes catalytiques à base de ruthénium Download PDF

Info

Publication number
EP2827986B1
EP2827986B1 EP13712897.1A EP13712897A EP2827986B1 EP 2827986 B1 EP2827986 B1 EP 2827986B1 EP 13712897 A EP13712897 A EP 13712897A EP 2827986 B1 EP2827986 B1 EP 2827986B1
Authority
EP
European Patent Office
Prior art keywords
titanium
catalyst
bis
dichloro
ruthenium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP13712897.1A
Other languages
German (de)
English (en)
Other versions
EP2827986A1 (fr
Inventor
Bastiaan WELS
Hans RIDDERIKHOFF
Tanja van BERGEN-BRENKMAN
Dessy LIMINTO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Croda International PLC
Original Assignee
Croda International PLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Croda International PLC filed Critical Croda International PLC
Publication of EP2827986A1 publication Critical patent/EP2827986A1/fr
Application granted granted Critical
Publication of EP2827986B1 publication Critical patent/EP2827986B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/128—Mixtures of organometallic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
    • C07C1/213—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by splitting of esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/373—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in doubly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/27—Preparation of carboxylic acid esters from ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/475—Preparation of carboxylic acid esters by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of groups between different molecules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/135—Compounds comprising a halogen and titanum, zirconium, hafnium, germanium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
    • C07C2531/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24 of the platinum group metals, iron group metals or copper
    • C07C2531/30—Halides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin

Definitions

  • the present invention relates to a process of self-metathesis of olefin comprising species, and in particular a method of self-metathesising unsaturated fatty acids or unsaturated fatty esters using ruthenium based catalysts and catalyst enhancer compounds.
  • Metathesis is a known chemical process in the art. The process typically involves catalytic reactions which result in the interchange of groups on either side of one or more carbon-carbon double bonds in a first molecule with groups on a second unsaturated molecule. Metathesis can therefore be adapted to oleochemical feedstocks. This group interchange takes place as a result of the formation and cleavage of the carbon-carbon double bonds aided by a catalyst.
  • Hoveyda-Grubbs olefin metathesis catalysts are known from US 2011/0160472 and Int. J. Mo. Sci. 2011, 12, 3989-3997 .
  • the existing catalysts may provide long reaction times (i.e. time for the reaction to reach equilibrium) usually of the order of several hours. This is exemplified in published patent application US 2011/0171147 . Longer reaction times can reduce the freedom of the reaction process design, the ability of the reaction operator to further process the reaction product, and the overall efficiency of the process especially where several batch runs or even continuous operation of the process is desired. Additionally, a further disadvantage of existing self-metathesis catalysts is that they can be liable to loss of catalytic activity over time due to catalyst degradation.
  • the catalysts described in published patent application WO 02/14376 allow for recovery of the catalyst at the end of the reaction, with subsequent re-use. This can be an important factor as the catalysts concerned are typically highly expensive.
  • the disclosed catalysts have the disadvantage of exhibiting losses of around 10% per reaction cycle.
  • the present invention therefore seeks to provide a process of self-metathesis for producing unsaturated dibasic acids and esters, and in particular using unsaturated fatty acids or esters as starting materials, where the process exhibits improved performance, and which reduces or overcomes at least some of the disadvantages of the prior attempts as described herein.
  • a catalyst enhancer compound to at least double the efficiency of the catalyst compound of Formula (I) or (II) defined herein, in the self-metathesis process defined herein.
  • Catalysts of general Formula (I) or (II) defined herein allow for faster reaction times and/or improved performance of self-metathesis reactions for unsaturated dicarboxylic fatty diacids and/or unsaturated dicarboxylic fatty diesters. Use of these catalysts also allows for lower concentrations of catalysts to be used in the self-metathesis process.
  • the terms 'metathesise' and 'metathesising' refer to the reacting of a feedstock in the presence of a metathesis catalyst to form a metathesis product comprising a new olefinic compound.
  • self-metathesis reaction comprises reacting of the carbon-carbon double bonds on the two identical molecules.
  • self-metathesis also refers to reaction of two carbon-carbon double bonds, each of which is present in identical subunits of a larger molecule.
  • An example would be the reaction between two identical unsaturated fatty acids linked together as part of a single triglyceride molecule.
  • self-metathesis may refer to reacting two of the same triglycerides present in a natural feedstock in the presence of a metathesis catalyst, wherein each triglyceride has an unsaturated carbon-carbon double bond, thereby forming two new olefinic molecules which may include a dimer of the triglyceride.
  • 'catalyst' refers to a compound that facilitates the reaction of interest, in this case self-metathesis, by lowering the rate-limiting free energy of the transition state of the reaction resulting in a larger reaction rate at the same temperature. However, unlike other reagents of the reaction, the catalysts are not consumed by the overall reaction itself.
  • the use of the term 'catalyst' in relation to the process of the present invention shall refer to catalyst compounds of Formula (I) or (II).
  • Homogeneous metathesis catalysts typically function by dissociation of one or more ligands in solution (the initiating step), which generates the actual productive catalytic species. Strictly speaking the catalyst compounds of Formula (I) or (II) described herein are thus precatalysts. Since the concentration and nature of the actual catalytic species cannot generally be accurately determined, no distinction is commonly made and the two terms can be used interchangeably.
  • the neutral ligand L may represent a phosphine.
  • said phosphine has formula -P(R 3 )(R 4 )(R 5 ), wherein R 3 , R 4 , and R 5 each independently represent C 1 to C 6 alkyl, C 5 or C 6 cycloalkyl, or aryl.
  • C 1 to C 6 alkyl' refers to saturated hydrocarbon radicals being straight chain, branched, cyclic, polycyclic moieties, or combinations thereof, containing from 1 to 6 carbon atoms.
  • the C 1 to C 6 alkyl may be optionally substituted.
  • suitable substituents may comprise hydroxy, halo, nitro, or amine groups.
  • R 3 , R 4 , and R 5 represent C 1 to C 6 alkyl
  • said alkyl may be independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2 methyl-butyl, pentyl, hexyl, cyclohexyl, or the like.
  • 'halo' refers to halide radicals derived from elements in Group VII (Group 17) of the periodic table.
  • the halide radicals may be independently selected from fluoro, chloro, bromo, or iodo.
  • said halo is selected from fluoro or chloro.
  • 'aryl' refers to an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and includes any monocyclic, bicyclic, or polycyclic carbon ring of up to 7 members in each ring, wherein at least one of the rings is aromatic. These aryl radicals may optionally be substituted. Examples of suitable substituents comprise hydroxy, C 1 to C 6 alkoxy, halo, nitro, amines, or C 1 to C 6 alkyl groups.
  • R 3 , R 4 , and R 5 represent aryl
  • said aryl may be independently selected from phenyl, p-tolyl, chlorophenyl, nitrophenyl, aminophenyl, methyl-aminophenyl, hydroxyphenyl, methyl-hydroxyphenyl, naphthyl, amino-naphthyl, tetrahydronaphthyl, indanyl, biphenyl, phenanthryl, anthryl, or the like.
  • R 3 , R 4 , and R 5 each independently represent C 5 or C 6 cycloalkyl, or aryl. More preferably, R 3 , R 4 , and R 5 each independently represent C 5 or C 6 cycloalkyl. Most preferably, the neutral ligand may be -P(Cy) 3 in which R 3 , R 4 , and R 5 each represent cyclohexyl ('Cy').
  • the neutral ligand L may be selected from a ligand of any of formulas L 1 , L 2 , L 3 , L 4 , or L 5 ;
  • R 9 , R 10 , and R 11 each independently represent hydrogen, C 1 to C 6 alkyl, C 2 to C 6 alkenyl, aryl, or halo. Any adjacent group of R 9 , R 10 , and R 11 may form a 3, 4, 5, 6, or 7 membered cycloalkyl, alkylene bridge, or aryl.
  • R 9 , R 10 , and R 11 represent C 1 to C 6 alkyl
  • said alkyl may be independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2 methyl-butyl, pentyl, hexyl, cyclohexyl, or the like.
  • the alkenyl radicals may be straight chain, branched, cyclic, polycyclic moieties, or combinations thereof.
  • the alkenyl radicals may each contain from 2 to 6 carbon atoms.
  • the C 2 to C 6 alkenyl may be optionally substituted. Examples of suitable substituents may comprise hydroxy, halo, nitro, or amine groups.
  • R 9 , R 10 , and R 11 represent C 2 to C 6 alkenyl
  • said alkenyl may be independently selected from vinyl, allyl, isopropenyl, pentenyl, hexenyl, cyclopentenyl, 1-propenyl, 2-butenyl, 2-methyl-2-butenyl, isoprenyl, and the like.
  • the alkylene bridge may preferably be formed from a C 2 to C 6 alkenyl, where said alkenyl is as defined herein.
  • R 9 , R 10 , and R 11 represent aryl
  • said aryl may be independently selected from phenyl, p-tolyl, chlorophenyl, nitrophenyl, aminophenyl, methyl-aminophenyl, hydroxyphenyl, methyl-hydroxyphenyl, naphthyl, amino-naphthyl, tetrahydronaphthyl, indanyl, biphenyl, phenanthryl, anthryl, or the like.
  • R 9 , R 10 , and R 11 each independently represent hydrogen or C 1 to C 6 alkyl. More preferably, R 9 , R 10 , and R 11 each independently represent hydrogen, methyl, ethyl, or butyl. Most preferably, R 9 , R 10 , and R 11 each independently represent hydrogen.
  • n represents an integer in the range from 1 to 3.
  • p represents an integer in the range from 0 to 4.
  • R 7 and R 8 each independently represent hydrogen, C 1 to C 6 alkyl, or aryl. More preferably, R 7 and R 8 each independently represent C 1 to C 6 alkyl or aryl. Most preferably, R 7 and R 8 each independently represent aryl.
  • R 7 and R 8 may represent identical groups.
  • R 7 and/or R 8 represent aryl
  • said aryl may preferably comprise an aryl substituted by from any of 1 to 5 independently selected groups, more preferably either 2 or 3 groups.
  • Said substituent groups may preferably be selected from C 1 to C 6 alkyl, C 1 to C 6 alkoxy, or halo. More preferably, said substituent groups are C 1 to C 6 alkyl. Most preferably, said substituent groups are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2 methyl-butyl, pentyl, hexyl, or cyclohexyl. Particularly preferred substituent groups may be methyl or isopropyl.
  • R 7 and R 8 both represent identical aryl groups comprising 2 or 3 C 1 to C 6 alkyl substituent groups. More preferably, R 7 and R 8 are each mesistyl (1,3,5-trimethylphenyl) or 2,6-diisopropylphenyl.
  • R 1 represents hydrogen or C 1 to C 6 alkyl. More preferably, R 1 represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or 2 methyl-butyl. Most preferably, R 1 represents hydrogen or methyl. Particularly preferred is where R 1 represents hydrogen.
  • a, b, c, d each independently represent hydrogen, C 1 to C 6 alkyl, aryl, or an electron withdrawing group.
  • said C 1 to C 6 alkyl and aryl may be as previously defined herein with regard to R 3 .
  • EWG 'electron withdrawing group'
  • said EWG may be selected from -NO 2 , C 1 to C 6 sulphonamides (-SO 2 NR 12 R 13 ), halo, C 1 to C 6 carbonyl, amine (-NR 12 R 13 R 14 ), amido (-C(O)NR 12 R 13 ), carbamate (-OC(O)NR 15 R 16 ), or-NR 17 C(O)R 18 .
  • the EWG is selected from -NO 2 sulphonamides (-SO 2 NR 12 R 13 ), or -NR 17 C(O)R 18 . More preferably, the EWG is -NR 17 C(O)R 18 .
  • R 12 , R 13 , and R 14 each independently represent hydrogen, C 1 to C 6 alkyl, C 1 to C 6 perhalogenoalkyl, C 1 to C 6 alkoxy, or halo.
  • R 15 , R 16 , R 17 , and R 18 each independently represent hydrogen, C 1 to C 6 alkyl, C 1 to C 6 alkoxy, C 1 to C 6 perhalogenoalkyl, C 1 to C 6 carbonyl, optionally substituted amide, nitrile, aryl, pyridinium alkyl, pyridinium perhalogenoalkyl, optionally substituted C 5 or C 6 cyclohexyl, or ester of a C 1 to C 6 alkyl.
  • R 15 , R 16 , R 17 , and R 18 each independently represent hydrogen, C 1 to C 6 alkyl, C 1 to C 6 alkoxy, C 1 to C 6 perhalogenoalkyl, C 1 to C 6 carbonyl, or ester of a C 1 to C 6 alkyl.
  • R 17 represents hydrogen or C 1 to C 6 alkyl. Most preferably, R 17 represents hydrogen.
  • R 15 , R 16 , and R 18 each independently represent C 1 to C 6 alkyl, C 1 to C 6 alkoxy, C 1 to C 6 perhalogenoalkyl, C 1 to C 6 carbonyl, or ester of a C 1 to C 6 alkyl.
  • R 15 , R 16 , and R 18 represent C 1 to C 6 alkoxy, C 1 to C 6 perhalogenoalkyl, or ester of a C 1 to C 6 alkyl.
  • 'perhalogenoalkyl refers to a radical derived from saturated hydrocarbon being straight chain, branched, cyclic, polycyclic moieties, or combinations thereof, containing 1 to 6 carbon atoms, and wherein at least one hydrogen is substituted by fluoro, chloro, bromo, or iodo.
  • all hydrogens are substituted by fluoro, chloro, bromo, or iodo.
  • all the hydrogens are substituted by fluoro.
  • the perhalogenalkyl group represents trifluoromethyl (-CF 3 ), trichloromethyl (-CCl 3 ), hexafluoroisopropyl (-CH(CF 3 ) 2 ), heptafluoroisopropyl (-CF(CF 3 ) 2 ), or heptafluoroethyl (-CF 2 CF 3 ). More preferably, the perhalogenalkyl group represents hexafluoroisopropyl (-CH(CF 3 ) 2 ), heptafluoroisopropyl (-CF(CF 3 ) 2 ), ortrifluoromethyl (-CF 3 ). Most preferably, the perhalogenalkyl group is trifluoromethyl (-CF 3 ).
  • alkoxy' refers to alkyl groups linked to oxygen which form an alkoxy radical having the structure -O-R 19 , and which are bonded to an adjacent radical via the oxygen.
  • R 19 represents a C 1 to C 6 alkyl group as defined herein.
  • alkoxy radicals may be independently selected from methoxy, ethoxy, butoxy, propoxy, amyloxy, cyclohexoxy, or the like.
  • R 15 , R 16 , R 17 and/or R 18 are a C 1 to C 6 alkoxy, preferably they each independently represent methoxy, ethoxy, butoxy, or propoxy. More preferably, ethoxy, butoxy, or propoxy. Most preferably, isobutoxy or isopropoxy.
  • the ester of a C 1 to C 6 alkyl is selected from methyl ester, ethyl ester, propyl ester, butyl ester. More preferably, methyl ester or ethyl ester. Most preferably, ethyl ester.
  • any of groups a, b, c, or d may be bonded to either group R 2 in general structure (I) or R 23 in general structure (II). In such an embodiment, any of groups a, b, c, or d may form a cyclic structure with either group R 2 in general structure (I) or R 23 in general structure (II).
  • the groups a, b, c, or d which forms the cyclic structure may represent any of the aforementioned substituents as defined herein.
  • the group which forms the cyclic structure may be an EWG, and most preferably may be -NR 17 C(O)R 18 .
  • R 17 may preferably be selected from hydrogen, C 1 to C 6 alkoxy, ester of a C 1 to C 6 alkyl, and R 18 may preferably be selected from C 1 to C 6 alkyl.
  • the cyclic structure may be formed by any of the atoms in the groups a, b, c, or d bonding to the oxygen to which either R 2 or R 23 would otherwise be bonded.
  • substituent d forms the cyclic structure.
  • R 2 represents hydrogen, C 1 to C 6 alkyl, C 1 to C 6 alkoxy, alkanone, or C 5 or C 6 cyclohexyl. More preferably, R 2 represents C 1 to C 6 alkyl, C 1 to C 6 alkoxy, or alkanone. Most preferably, R 2 represents C 1 to C 6 alkyl or an alkanone.
  • 'alkanone' refers to a carbonyl comprising group -(CHR 20 ) n C(O)R 21 where R 20 and R 21 are selected from hydrogen, C 1 to C 6 alkyl, or C 5 to C 6 cycloalkyl, and where n represents an integer in the range from 1 to 5.
  • R 20 and R 21 each independently represent hydrogen, methyl, or ethyl, and n represents the integer 1. More preferably, R 20 and R 21 both represent methyl, and n represents the integer 1.
  • 'aryloxy' refers to aryloxy radicals having the structure -O-Ar, and which are bonded to an adjacent radical via the oxygen.
  • Ar represents an aryl group as defined herein.
  • aryloxy radicals may be independently selected from phenoxy, naphthyloxy, phenylphenoxy, diphenylphenoxy, triphenylphenoxy, or tetraphenylphenoxy.
  • 'arylalkoxy' refers to arylalkoxy radicals having the structure -O-R 22 -Ar, and which are bonded to an adjacent radical via the oxygen.
  • R 22 represents a C 1 to C 6 alkyl and Ar represents an aryl group, both as defined herein.
  • arylalkoxy radicals may be independently selected from phenylmethoxy, phenylethoxy, naphthlymethoxy, and naphthlyethoxy.
  • R 2 is C 1 to C 6 alkyl
  • R 2 may preferably be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl. More preferably, selected from methyl, ethyl, n-propyl, or isopropyl. Most preferably, R 2 is isopropyl.
  • R 23 represents hydrogen, C 1 to C 6 alkyl, C 1 to C 6 alkoxy, alkanone, or C 5 or C 6 cyclohexyl. More preferably, R 23 represents C 1 to C 6 alkyl, or C 1 to C 6 alkoxy. Most preferably, R 23 represents C 1 to C 6 alkoxy. In particular, R 23 may be selected from hydrogen, methyl, ethyl, propyl, methoxy, ethoxy, butoxy, propanoxy, amyloxy, cyclohexoxy, or the like. Preferably, R 23 may be selected from methoxy, ethoxy, or butoxy. Most preferably, R 23 is methoxy.
  • self-metathesis catalysts of general structure (I) are disclosed in WO 2008/065187 and WO 2008/034552 .
  • Catalysts having general Formula (I) which are according to the invention are selected from:
  • a particularly preferred example of a suitable catalyst of general Formula (II) may be selected from: wherein Mes represents mesityl group.
  • the particularly preferred examples of suitable catalysts that may be used are available commercially from Umicore of Hanau-Wolfgang,Germany.
  • the starting materials for the self-metathesis process of the present invention comprise unsaturated carboxylic fatty acids and/or esters of unsaturated carboxylic fatty acids.
  • Suitable unsaturated carboxylic fatty acids may be mono- or polyunsaturated carboxylic acids having in the range from 14 to 24 carbon atoms (including the carbonyl carbon atom).
  • Unsaturated carboxylic acids may be represented by the following formula R 24 -COOH, wherein R 24 represents a mono- or polyunsaturated alkenyl radical having in the range from 14 to 24 carbon atoms (including the carbonyl carbon atom).
  • alkenyl' refers to hydrocarbon radicals having at least one or a plurality, preferably no more than 6, double bonds.
  • the alkenyl radicals may be straight chain, branched, cyclic, polycyclic moieties, or combinations thereof.
  • the alkenyl radicals may be optionally substituted with a hydroxy, fluoro, chloro, bromo, iodo, nitro, amines, or amides.
  • R 24 is preferably acyclic.
  • R 24 is a straight chain alkenyl, and therefore unbranched.
  • R 24 is an acyclic and straight chain alkenyl.
  • R 24 are alkenyls having in the range from 1 to 3 carbon-carbon double bonds. Most preferred are mono-unsaturated alkenyl radicals.
  • the carbon-carbon double bond of the fatty chain may be present either in a cis or a trans configuration.
  • Suitable polyunsaturated carboxylic acids are, for example, linoleic acid [18:2 (9,12); (9Z-12Z)-octadeca-9,12-dienoic acid], alpha-linolenic acid [18:3 (9,12,15); (9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid], gamma-linolenic acid [18:3 (6,9,12); (6Z,9Z,12Z)-octadeca-6,9,12-trienoic acid], calendic acid [18:3 (8,10,12); (8E,10E,12Z)-octadeca-8,10,12-trienoic acid], punicic acid [18:3 (9,11,13); (9Z,11E,13Z)-octadeca-9,11,13-trienoic acid], alpha-eleostearic acid [18:3 (9,11,13); (9Z,
  • Monounsaturated carboxylic acids are preferred.
  • monounsaturated carboxylic acids selected from oleic acid [18:1 (9); (9Z)-octadeca-9-enoic acid], elaidic acid [18:1 (tr9); (9E)-octadeca-9-enoic acid], erucic acid [22:1 (13); (13Z)-docosa-13-enoic acid], and brassidic acid [22:1 (tr13); (13E)-docosa-13-enoic acid] are preferred.
  • esters of unsaturated carboxylic fatty acids for use in the self-metathesis process of the present invention comprise esters of the unsaturated carboxylic acids as defined herein.
  • esters are those formed from unsaturated carboxylic acids, as defined herein, with alcohols represented by the following formula R 25 -OH.
  • R 25 represents C 1 to C 14 alkyl, C 1 to C 14 alkenyl, or C 1 to C 14 aryl radical.
  • the C 1 to C 14 alkyl, C 1 to C 14 alkenyl, or C 1 to C 14 aryl radicals may optionally comprise one or more substituents, said substituents selected from hydroxy, C 2 to C 6 alkenyl, C 1 to C 6 alkyl, C 1 to C 6 alkoxy, fluoro, chloro, bromo, iodo, nitro, or aryl.
  • R 25 may, by way of example, represent methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylpropyl, pentyl, 2,2-dimethylpropyl, 2-methylbutyl, 3-methylbutyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpenyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, heptyl, octyl, phenyl, methoxyphenyl, dimethoxyphenyl, chlorophenyl, nitrophenyl, ethenyl, propenyl, or butenyl radicals.
  • R 25 may preferably represent methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl.
  • ester starting materials may be methyl oleate, ethyl oleate, or isopropyl oleate.
  • Suitable ester starting materials may also include esters of the mono- or polyunsaturated carboxylic acids, as defined herein, with glycerol (glycerol esters).
  • Glycerol esters may be selected from glycerol monoesters (monoglycerides, monoacylglycerol), glycerol diesters (diglycerides, diacyl glycerol), and also glycerol triesters (triglycerides, triacylglyceryl), or combinations thereof.
  • the unsaturated carboxylic acids or the esters of the unsaturated carboxylic acids as used for the self-metathesis process may be homogeneous in that the starting material is comprised of only one specific acid or ester selected from the above listed groups.
  • the starting material may be heterogeneous in that it comprises a mixture, either as a mixture of a number of different acids or a number of different esters, or as a mixture of acids and esters.
  • the starting materials are most often derived from natural oils, and as such usually the fatty acid component of the starting material (either in the form of a free acid or as the various esters) will consist of multiple similar constituents depending on the source of the fatty acid.
  • the fatty acid components are at least 60 wt.% of a single identity. More preferably, at least 80 wt.% of a single identity. Most preferably, at least 90 wt.% of a single identity.
  • the self-metathesis process according to the invention may be carried out at temperatures in the range of from 0°C to 140°C, preferably in the range of from 25°C to 120 °C, more preferably in the range of from 60 °C to 100°C.
  • the temperature of the self-metathesis process may represent an important factor in maximising conversion, with each catalyst and starting material having a preferred optimum temperature.
  • the process may be undertaken in customary solvents in which the starting materials and the catalyst dissolve.
  • suitable solvents may be those based upon hydrocarbons or alcohols.
  • the method can be carried out without a solvent.
  • the self-metathesis process is an equilibrium reaction wherein the position of the equilibrium between unreacted unsaturated carboxylic acids and/or esters of the feedstock, and reacted dicarboxylic acids and diesters may vary depending on a number of factors including feedstock properties, catalyst used, and other process conditions. It is noted that different natural oil feedstocks may have different maximum theoretical conversion limits.
  • the level of conversion for the self-metathesis process of the present invention is therefore defined as the weight percentage of the acid or ester in the starting material which has been consumed by the reaction process and reacted to form the respective diacid or diester at the point when the process has reached equilibrium.
  • a level of conversion and equilibrium a closed batch process system should be considered.
  • the level of conversion of the present process is at least 30 wt.%. More preferably, the level of conversion of the process is at least 35 wt.%. Even more preferably, the level of conversion of the process is at least 40 wt.%. Further preferably, the level of conversion of the process is at least 45 wt.%. More preferably, the level of conversion of the process is at least 50 wt.%. Particularly preferred is a conversion level of at least 55 wt.%. A conversion level for the process of at least 60 wt.% may be preferred under optimal conditions.
  • the time to reach equilibrium is preferably less than 1 hour, more preferably less than 30 minutes, even more preferably less than 20 minutes, further preferably less than 10 minutes, particularly preferably less than 5 minutes, particularly advantageously less than 2 minutes, and most preferably less than 1 minute.
  • the time to reach equilibrium may be more than 0.5 seconds, more than 1 second, and more than 5 seconds.
  • the concentration of catalyst required in order to achieve equilibrium for the self-metathesis process is preferably less than 200 ppm, more preferably less than 100 ppm, more preferably 50 ppm, more preferably less than 30 ppm, even more preferably less than 20 ppm, further preferably less than 10 ppm, particularly preferably less than 5 ppm, and most preferably less than 4 ppm.
  • the concentration of catalyst required in order to achieve the level of conversion for the self-metathesis process may be more than 0.01 ppm, preferably more than 1 ppm, more preferably more than 2 ppm, even more preferably more than 3 ppm.
  • a particularly preferred concentration of catalyst required to achieve the level of conversion, and therefore the time to reach equilibrium, is between 3 and 5 ppm.
  • the level of conversion and reaction times of the self-metathesis process may be determined by the GC-analysis of the reaction products, as described herein.
  • the 'catalyst efficiency' is defined as the time taken for the reaction process to reach equilibrium (in minutes) as a function of the amount of catalyst present (i.e. per ppm of catalyst). Therefore, a value for catalyst efficiency for any specific reaction can be calculated by multiplying time taken for the reaction process to reach equilibrium (in minutes) by the concentration of catalyst used (in ppm). For example, if equilibrium is reached in 1 minute with a concentration of 3 ppm of catalyst, the catalyst efficiency value will be 3.
  • the catalyst efficiency for the self-metathesis process according to the present invention is preferably less than 500, more preferably less than 200, even more preferably less than 100, further preferably less than 70, particularly preferably less than 50, more preferably less than 30, even more preferably less than 20, further preferably less than 10, most preferably less than 3.
  • turnover frequency This provides an indication of the number of reactions per unit of time (per second typically). This would relate to the value of time taken for the reaction process to reach equilibrium (in minutes) which is used in calculating catalyst efficiency as described above.
  • the turnover frequency may therefore be defined as the turnover number divided by reaction time in seconds.
  • the effective turnover frequency of the catalyst for the self-metathesis process according to the invention is suitably in the range from 10 to 50,000.
  • the turnover frequency is in the range from 5,000 to 20,000. More preferably, the turnover frequency is in the range from 5,000 to 15,000.
  • the catalyst may be able to catalyse a number of reactions without being subjected to regeneration. This may be particularly advantageous when performing the metathesis reaction in a continuous system where multiple reaction cycles are done.
  • a known term of art is effective turnover number. This provides an indication of the number of molecules of starting material, e.g. methyl oleate converted to products per molecule of the catalyst precursor. Effective turnover numbers are calculated by dividing the number of moles of starting material converted by the number of moles of catalyst.
  • the turnover number of the catalyst for the self-metathesis process according to the invention is suitably in the range from 5,000 to 1,000,000.
  • the turnover number is in the range from 20,000 to 500,000. More preferably, the turnover number is in the range from 200,000 to 350,000.
  • Catalyst stability may be defined as the time the catalyst remains stable and able to undertake the catalysis of the self-metathesis reaction. Catalysts would be considered no longer stable once they are unable to be recycled or re-used.
  • the catalyst stability for the self-metathesis process according to the invention is suitably greater than 5 minutes. Preferably, greater than 15 minutes. More preferably, greater than 60 minutes of use.
  • Catalyst activity is defined as the ability of the catalyst to continue catalysing the reaction at a certain speed. Catalyst activity values are expressed as the percentage retention of activity. For example, 100% retention of activity means that the same degree of conversion occurs on a second or subsequent reaction cycle as occurred on the first reaction cycle.
  • the catalyst may for example be able to catalyse the metathesis reaction to over 90% of the equilibrium level of conversion within 2 minutes under certain reaction conditions.
  • the catalyst activity is deemed unchanged if it is able to catalyse a freshly added amount of starting material to within the same theoretical conversion in the same time.
  • the catalyst for the self-metathesis process according to the invention is sufficiently stable to retain over 50% of its activity after 30 minutes use. More preferably, the catalyst will be able to retain over 75% of its activity after 30 minutes. Most preferably, the catalyst will be able to retain over 85% of its activity after 30 minutes.
  • the catalyst activity is suitably measured under continuous reaction conditions.
  • the term 'catalyst poison' includes any chemical species or impurity in a feedstock that reduces or is capable of reducing the functionality (e.g. efficiency, conversion, turnover number) of the metathesis catalyst compounds of Formula (I) or (II).
  • the catalyst poisons may be peroxides, including any and all peroxides, such as hydrogen peroxides, or may be non-peroxide poisons or other catalyst poisons which may include catalyst poisons other than peroxides that may be found in, for example, natural oil feedstocks.
  • These non-peroxide poisons include, but are not limited to, water, aldehydes, alcohols, by-products from oxidative degradation, terminal conjugated polyenes, free fatty acids, free glycerin, aliphatic alcohols, nitriles, esters with unsaturated groups adjacent to ester groups, d-sphingosine, amines, sulphur containing compounds, phosphorous containing compounds, and additional impurities.
  • the process of the invention does not include any chemical treatment of the feedstock or starting material in order to remove catalyst poisons.
  • An antioxidant may be added to the starting material, preferably in the range from 0.1 ppm to 50 ppm, more preferably in the range from 0.5 ppm to 20 ppm, most preferably in the range from 1 ppm to 10 ppm.
  • Suitable antioxidants may be selected from t-butylhydroquinone (TBHQ) or butylated hydroxytoluene (BHT), dihydroxytoluene, stearic hydrazide, or 2,6-di-tert-butyl-4-methylphenol.
  • TBHQ t-butylhydroquinone
  • BHT butylated hydroxytoluene
  • dihydroxytoluene dihydroxytoluene
  • stearic hydrazide 2,6-di-tert-butyl-4-methylphenol.
  • 2,6-di-tert-butyl-4-methylphenol 2,6-di-tert-butyl-4-methylphenol.
  • the antioxidant may be TBHQ.
  • Said antioxidants have been found to enhance the oxidative stability, reduce or prevent formation of poisons, and increase shelf life of the starting material prior to use in the self-metathesis process.
  • the antioxidant may be added to the starting material when the starting material is manufactured.
  • the level of catalyst poisons formed in the starting material may be kept at a relatively low level, such that there is no need to remove catalyst poisons before performing the metathesis reaction.
  • the formation of peroxide in the starting material may be at least partially inhibited due to the presence of an antioxidant.
  • an antioxidant therefore prevents formation of catalyst poisons, and may therefore be an advantageous step when compared to allowing the poisons to form and subsequently treating the starting material before use to cause their removal.
  • the starting material for the self-metathesis process according to the present invention may comprise a level of peroxide of less than 5 meq/kg. More preferably, the level of peroxide may be less than 3 meq/kg. More preferably, the level of peroxide may be less than 2 meq/kg. Most preferably, the level of peroxide may be less than 1 meq/kg.
  • the water content of the starting material for the self-metathesis process may be less than 0.1 wt%.
  • the water content is less than 0.05 wt%. More preferably, the water content is less than 0.04 wt%. Most preferably, the water content is less than 0.03 wt%.
  • the hydroxyl value of the starting material for the self-metathesis process may be less than 0.1 mg(KOH).g -1 .
  • the hydroxyl value is less than 0.05 mg(KOH).g -1 .
  • the hydroxyl value is less than 0.04 mg(KOH).g -1 .
  • the hydroxyl value is less than 0.03 mg(KOH).g -1 .
  • Hydroxyl Values were measured using a method based upon BS 684 Section 2.9 (1976) and results are quoted in mg(KOH).g -1 (sample) and are corrected for the contribution of acid OH groups.
  • the acid value of the starting material for the self-metathesis process may be less than 0.20 mg(KOH).g -1 .
  • the acid value is less than 0.10 mg(KOH).g -1 . More preferably, the acid value is less than 0.05 mg(KOH).g -1 .
  • the acid value was measured using the A.O.C.S. Official method Te 1a-64 (Reapproved 1997), and expressed as the number of milligrams of potassium hydroxide required to neutralise the free fatty acids in one gram of sample.
  • the water content, hydroxyl value, and acid value of the starting material are all within the ranges defined herein. Values which are above the ranges defined herein may result in reduced reaction performance and/ or catalyst poisoning.
  • the self-metathesis process according to the present invention additionally comprise the presence of a catalyst enhancer compound as defined in the appended claims.
  • Said catalyst enhancer compound reacts with catalyst poisons in preference to the reaction of the poisons with the catalyst compounds defined herein and used in the process according to the present invention.
  • the catalyst enhancer compounds preferably do not take part, and are not consumed, in the self-metathesis reaction.
  • the catalyst enhancer compound is selected from boron trifluoride, boron trichloride, boron triiodide, boron tribromide, and most preferably is boron trifluoride.
  • the catalyst enhancer compound is selected from titanium compounds having the general formula Ti.[Q] 4 wherein each Q independently represents hydrogen, a C 1 to C 10 alkoxy group, a halide, a C 12 to C 18 fatty alcohol or a C 6 to C 18 fatty acid.
  • Said C 1 to C 10 alkoxy group refers to alkyl groups linked to oxygen which form an alkoxy radical, and which are bonded to the titanium atom via the oxygen.
  • the C 1 to C 10 alkyl may be optionally substituted for example by hydroxyl groups, and may optionally consist of more than one covalently linked alkoxy radical.
  • Said C 1 to C 10 alkyl may be independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2 methyl-ethyl, 2 methyl-propyl, 2 methyl-butyl, 2 methyl-pentyl, 2 methyl hexyl, 2 methyl-heptanyl, 2 methyl-octyl, 2 ethyl-propyl, 2 ethyl-butyl, 2 ethyl-pentyl, 2 ethyl-hexyl, 2 ethyl-heptanyl, 2-ethyl-1,3-hexanediol, pentyl, hexyl, cyclohexyl, or the like.
  • said C 1 to C 10 alkyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2 methyl-pentyl, 2 methyl hexyl, 2 ethyl-pentyl, or 2 ethyl-hexyl.
  • said C 1 to C 10 alkyl is selected from ethyl or 2 ethyl-hexyl.
  • the C 6 to C 18 fatty acid may be selected from linear or branched unsaturated fatty acids.
  • the unsaturated fatty acids may be selected from fatty acids having either a cis/trans configuration, and may have one or more than one unsaturated double bonds.
  • the fatty acids used are linear monounsaturated fatty acids.
  • Suitable C 6 to C 18 fatty acids are preferably selected from caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, or palmitic acid. More preferably, caprylic acid or lauric acid.
  • the titanium based compounds may comprise bidentate Q ligands, e.g. covalently linked multiple alkoxy radicals.
  • bidentate Q ligands e.g. covalently linked multiple alkoxy radicals.
  • examples include titanium (IV) oxyacetylacetonate and titanium diisopropoxidebis(2,2,6,6-tetramethyl-3,5-heptanedionate).
  • titanium based compounds having general formula Ti.[Q] 4 may be selected from titanium (IV) methoxide, titanium (IV) ethoxide, titanium (IV) propoxide, titanium (IV) isopropoxide, titanium (IV) butoxide, titanium (IV) tert-butoxide, titanium (IV) 2-ethylhexoxide, titanium (IV) 2-ethyl-1,3-hexanediolate, titanium (IV) tetrachloride, titanium (IV) tetrabromide, titanium (IV) tetrafluoride, and titanium (IV) tetraiodide.
  • the titanium based compounds are selected from titanium (IV) isopropoxide, titanium (IV) ethoxide, titanium (IV) 2-ethylhexoxide.
  • the catalyst enhancer compound may be added during the reaction process, prior to the start of the process, or alternatively at the same time the catalyst is added. In a preferred embodiment, the catalyst enhancer compound is added substantially simultaneously with the metathesis catalyst at the start of the reaction.
  • an amount of between 10 ppm and 1,000 ppm of the catalyst enhancer compound is added to the reaction mixture, more preferably an amount between 50 ppm and 300 ppm is added, and most preferably 150 ppm and 250 ppm is added.
  • the catalyst enhancer may be added to the reaction mixture such that the ratio of the number of moles of the non-catalyst enhancer to number of moles of poison is in the range from 2.5 to 10:1. Preferably, in the range from 3 to 8:1. More preferably, in the range from 3.5 to 7:1. Most preferably, in the range from 4 to 6:1.
  • the catalyst enhancer compound provides for lower levels of catalyst deactivation which therefore allows for lower concentrations of catalyst to be used to achieve the same conversion over time, thereby achieving improved levels of catalyst efficiency. Therefore, with addition of a catalyst enhancer compound, the level of catalyst used in the self-metathesis process according to the invention may preferably be less than 10 ppm, more preferably less than 5 ppm, and most preferably less than 4 ppm.
  • the amount of catalyst can be reduced to half of the otherwise required loading for a certain conversion. More preferably a third, and most preferable a quarter or less of the catalyst is needed.
  • the effective efficiency of the catalyst can be at least doubled, at least tripled, or most preferably at least quadrupled by inclusion of a catalyst enhancer compound.
  • the catalyst efficiency, as defined herein, can be significantly improved in the presence of the catalyst enhancer compound such that the catalyst efficiency value of the catalyst is suitably reduced by at least 10%, preferably by an amount in the range from 20% to 99%, more preferably 50% to 90%, particularly 75% to 90%, and especially 80% to 90% compared to the same reaction in the absence of the catalyst enhancer compound.
  • the catalyst enhancer compound may be combined with antioxidant treatment of the starting material. Said combination may result in the ability to use low amounts of catalyst in the self-metathesis reaction with little or no increase in reaction time.
  • the self-metathesis process in accordance with the present invention produces unsaturated dicarboxylic acids and unsaturated dicarboxylic diesters, and also the corresponding unsaturated hydrocarbons.
  • the mixture can be separated, for example by distillation, fractional crystallisation, or extraction. If desired, the products obtained in this way can be subjected to hydrogenation.
  • the reaction products are not limited in the uses to which they can be applied.
  • reaction products might include use in sunscreen formulations, polymer building block, personal care formulations, lubricant formulations, as surfactants, or in waxes. All of the features described herein may be combined with any of the above aspects, in any combination.
  • all tests and physical properties listed have been determined at atmospheric pressure and room temperature (i.e. 20°C), unless otherwise stated herein, or unless otherwise stated in the referenced test methods and procedures. All reactions mentioned in the examples were performed under a nitrogen atmosphere. Before addition of the catalyst, nitrogen gas was bubbled through the reaction mixture while it was being heated to the reaction temperature, and at least for 15 minutes. Selected examples were performed where the reaction feedstock was purified by passing over 25 wt.% of Al 2 O 3 directly before performing the reaction to remove catalyst poisons.
  • Reaction conversion was measured by GC analysis. To ensure no further reaction took place between sampling the reaction mixture and measurement of GC, samples were quenched by addition of ethyl vinyl ether. Full conversion was measured by performing a single reaction with a very high loading of catalyst, which was known to drive the reaction to complete equilibrium. This mixture was thereafter used as a reference to determine relative GC peak heights at full conversion.
  • Examples 1-6 are not according to the present invention.
  • reaction mixture contained 24.8% 9-octadecene and 25.4% 9-octadecenedioic acid dimethyl ester. A catalyst efficiency value of 26 was achieved.
  • reaction equilibrium conversion After 30 seconds the reaction equilibrium conversion was reached.
  • the reaction mixture contained 25.3% 9-octadecene and 25.2% 9-octadecenedioic acid dimethyl ester. A catalyst efficiency value of 18.5 was achieved.
  • reaction equilibrium conversion After 30 seconds the reaction equilibrium conversion was reached.
  • the reaction mixture contained 25.1% 9-octadecene and 25.5% 9-octadecenedioic acid dimethyl ester. A catalyst efficiency value of 31.5 was achieved.
  • reaction equilibrium conversion After 30 seconds the reaction equilibrium conversion was reached.
  • the reaction mixture contained 20.6% 9-octadecene and 28.4% 13-hexacosanedioic acid dimethyl ester. A catalyst efficiency value of 52.5 was achieved.
  • reaction mixture contained 51.0% isopropyl oleate, 19.3% 9-octadecene and 23.0% 9-octadecenedioic acid diisopropyl ester. A catalyst efficiency value of 25 was achieved.
  • reaction equilibrium conversion was reached.
  • the reaction mixture contained 54.5% dodecyl oleate, 8.8% 9-octadecene and 36.7% 9-octadecenedioic acid di-dodecyl ester.
  • a catalyst efficiency value of 25 was achieved.
  • a comparative prior art catalyst as disclosed in US 2011/0171147 was also tested.
  • 100 ml methyl oleate purified by aluminium-oxide treatment
  • 250 ppm of ([1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidnyliden]-[2-[[(4-methylphenyl)imino]methyl]-4-nitrophenol]-[3-phenyl-1H-inden-1-ylidene] ruthenium(II)chlorid) was dissolved in 1 ml toluene, and this was added to the methyl oleate.
  • reaction mixture contained 20.6% dimethyldiester and 20.2% 9-octadecene.
  • a catalyst efficiency value in excess of 97,500 was found with the prior art catalyst.
  • Catalyst used was ([1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinyliden]dichloro[(2-isopropoxy)(5- isobutoxyacetamido)benzyliden]]ruthenium(II)). Improvements were seen on addition of catalyst enhancer compound. In Example 8 addition of 200 ppm gave 50% conversion whilst using only 5 ppm of catalyst. Example 8 used lower concentration of catalyst (3 ppm) which resulted in 46% conversion. Example 9 shows use of BF 3 as another catalyst enhancer compound with similar results.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Claims (5)

  1. Procédé d'autométathèse pour la production d'acides dicarboxyliques et/ou de diesters dicarboxyliques insaturés, dans lequel des acides carboxyliques insaturés ayant de 14 à 24 atomes de carbone et/ou des esters de tels acides carboxyliques insaturés réagissent en présence d'au moins un catalyseur choisi dans le groupe constitué des : [1,3-bis(2,6-diisopropylphényl)-2-imidazolidinylidène]dichloro[2-(1-méthylacétoxy)-phényl]méthylèneruthénium(II) ;
    [1,3-bis(2,4,6-triméthylphényl)-2-imidazolidinylidène]dichloro[2-(1-méthylacétoxy)phényl]méthylèneruthénium(II) ;
    [1,3-bis(2,6-diisopropylphényl)-2-imidazolidinylidène]dichloro[[2-(2-oxopropoxy)phényl]méthylène]ruthénium(II) ;
    [1,3-bis(2,4,6-triméthylphényl)-2-imidazolidinylidène]dichloro[[2-(2-oxopropoxy)phényl]méthylène]ruthénium(II) ;
    ([1,3-bis(2,4,6-triméthylphényl)-2-imidazolidinylidène]dichloro[(2-isopropoxy) (5-trifluoracétamido)benzylidène]ruthénium(II) ;
    ([1,3-bis(2,6-diisopropylphényl)-2-imidazolidinylidène]dichloro[(2-isopropoxy) (5-trifluoracétamido)benzylidène]]ruthénium(II)) ;
    ([1,3-bis(2,6-diisopropylphényl)-2-imidazolidinylidène]dichloro[(2-isopropoxy) (5-isobutoxyacétamido)benzylidène]]ruthénium(II)) ;
    ([1,3-bis(2,4,6-triméthylphényl)-2-imidazolidinylidène]dichloro[(2-isopropoxy) (5-isobutoxyacétamido)benzylidène]]ruthénium(II)) ;
    ([1,3-bis(2,6-diisopropylphényl)-2-imidazolidinylidène]dichloro[(2-isopropoxy) (5-éthylesteracétamido)benzylidène]]ruthénium(II)) ; et
    (chlorure de (1,3-bis(2,6-diisopropylphényl)-imidazolidin-2-ylidène) ((2-éthyl-3-oxo-3,4-dihydro-2H-benzo[b][1,4]oxazine)-8-yl)méthylène)ruthénium(II)) ; et
    le procédé comprend en outre la présence d'un composé activateur de catalyseur choisi parmi le trifluorure de bore, le trichlorure de bore, le triiodure de bore, le tribromure de bore ou des composés de titane ayant la formule générale Ti.[Q]4 dans laquelle chaque Q représente indépendamment hydrogène, un groupe alcoxy en C1 à C10, un halogénure, un alcool gras en C12 à C18 ou un acide gras en C6 à C18.
  2. Procédé selon la revendication précédente, dans lequel la concentration de catalyseur est inférieure à 100 ppm.
  3. Procédé selon l'une quelconque des revendications précédentes, dans lequel aucun traitement chimique de la matière première ou du matériau de départ pour éliminer les poisons de catalyseur n'est effectué.
  4. Procédé selon l'une quelconque des revendications précédentes dans lequel le matériau de départ d'acides carboxyliques insaturés et/ou d'esters d'acides carboxyliques insaturés comprend (i) un taux de peroxyde inférieur à 3 meq/kg, (ii) une teneur en eau inférieure à 0,05 % en poids, (iii) un indice d'hydroxyle inférieur à 0,05 mg (KOH) .g-1 et/ou (iv) un indice d'acide inférieur à 0,10 mg (KOH) .g-1.
  5. Procédé selon l'une quelconque des revendications précédentes, dans lequel le composé de titane est choisi dans le groupe constitué des méthoxyde de titane (IV), éthoxyde de titane (IV), propoxyde de titane (IV), isopropoxyde de titane (IV), butoxyde des titane (IV) tert-butoxyde de titane (IV), 2-éthylhexoxyde de titane (IV), 2-éthyl-1,3-hexanediolate de titane (IV), tétrachlorure de titane (IV), tétrabromure de titane (IV), tétrafluorure de titane (IV), tétraiodure de titane (IV) et des mélanges de ceux-ci.
EP13712897.1A 2012-03-18 2013-03-18 Métathèse d'oléfines avec des complexes catalytiques à base de ruthénium Active EP2827986B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB1204715.5A GB201204715D0 (en) 2012-03-18 2012-03-18 Metathesis of olefins using ruthenium-based catalytic complexes
PCT/GB2013/050684 WO2013140144A1 (fr) 2012-03-18 2013-03-18 Métathèse d'oléfines, à l'aide de complexes catalytiques à base de ruthénium

Publications (2)

Publication Number Publication Date
EP2827986A1 EP2827986A1 (fr) 2015-01-28
EP2827986B1 true EP2827986B1 (fr) 2018-10-24

Family

ID=46052095

Family Applications (2)

Application Number Title Priority Date Filing Date
EP13712897.1A Active EP2827986B1 (fr) 2012-03-18 2013-03-18 Métathèse d'oléfines avec des complexes catalytiques à base de ruthénium
EP13711121.7A Active EP2827985B1 (fr) 2012-03-18 2013-03-18 Procédé de métathèse

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP13711121.7A Active EP2827985B1 (fr) 2012-03-18 2013-03-18 Procédé de métathèse

Country Status (4)

Country Link
US (2) US9604903B2 (fr)
EP (2) EP2827986B1 (fr)
GB (1) GB201204715D0 (fr)
WO (2) WO2013140145A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014152309A1 (fr) * 2013-03-14 2014-09-25 Materia, Inc. Utilisation de sels métalliques solubles dans des réactions de métathèse
FR3024037B1 (fr) 2014-07-25 2018-03-02 Sederma Ingredient actif cosmetique ou dermatologique comprenant un melange d'acides dicarboxyliques gras insatures, compositions le comprenant et utilisations cosmetiques ou dermatologiques
US10316255B2 (en) * 2015-09-03 2019-06-11 The Governors Of The University Of Alberta Conversion of lipids into olefins
US10138430B2 (en) * 2015-09-03 2018-11-27 The Governors Of The University Of Alberta Conversion of lipids into olefins
EP3631440B1 (fr) * 2017-06-02 2023-02-22 Univation Technologies, LLC Procédé de détermination d'une diminution relative de l'efficacité catalytique d'un catalyseur dans une solution de catalyseur

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4654462A (en) * 1985-02-12 1987-03-31 Societe Nationale Elf Aquitaine Metathesis of olefins with a catalyst based upon a tungsten complex
WO2012143067A1 (fr) * 2011-04-20 2012-10-26 Cognis Ip Management Gmbh Procédé de préparation de composés insaturés

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4943397A (en) 1988-09-22 1990-07-24 Shell Oil Company Metathesis of functional olefins
CA2196061C (fr) 1992-04-03 2000-06-13 Robert H. Grubbs Complexes carbeniques de ruthenium et d'osmium a haute activite pour reactions de metathese des olefines, et leur procede de synthese
US5312940A (en) 1992-04-03 1994-05-17 California Institute Of Technology Ruthenium and osmium metal carbene complexes for olefin metathesis polymerization
US6388032B1 (en) 1997-10-16 2002-05-14 Teijin Limited Cyclic olefin polymer containing little catalyst residue
US6900347B2 (en) 1998-09-01 2005-05-31 Tilliechem, Inc. Impurity inhibition in olefin metathesis reactions
ATE438462T1 (de) 1998-09-10 2009-08-15 Univ New Orleans Foundation Katalysatorkomplex mit phenylindenyliden-ligand
DE60140455D1 (de) 2000-08-10 2009-12-24 Trustees Boston College Wiederverwendbare methathese-katalysatoren
WO2002076920A1 (fr) 2001-03-26 2002-10-03 Dow Global Technologies Inc. Metathese d'esters d'acides gras insatures ou d'acides gras insatures avec des olefines inferieures
DE60205444T2 (de) * 2001-12-06 2006-06-01 Kerr Corp., Orange Beschleuniger für Metathesekatalysator
DE60310521T2 (de) 2002-01-22 2007-11-08 Universiteit Gent Metallkomplexe für die metathese
CN101003459B (zh) 2002-10-24 2011-08-10 陶氏环球技术有限责任公司 烯烃易位产物混合物的稳定
GB0229770D0 (en) * 2002-12-20 2003-01-29 Sasol Technology Uk Ltd Olefinic metathesis in the presence of phenolic compounds
WO2005049668A1 (fr) * 2003-11-18 2005-06-02 Jsr Corporation Nouveau (co)polymere, son procede de production et procede de production d'un (co)polymere carboxyle
GB0514612D0 (en) 2005-07-15 2005-08-24 Sasol Technology Uk Ltd The use of a phosphorus containing ligand and a cyclic organic ligand in a metathesis catalyst
DE102006043704A1 (de) 2006-09-18 2008-03-27 Umicore Ag & Co. Kg Neue Metathesekatalysatoren
FR2909382B1 (fr) * 2006-11-30 2009-01-23 Enscr Complexes catalytiques a base de ruthenium et utilisation de tels complexes pour la metathese d'olefines
CA2695903C (fr) 2007-08-09 2015-11-03 Daniel W. Lemke Procedes chimiques pour traiter une matiere premiere de metathese
DE102007039526A1 (de) * 2007-08-21 2009-02-26 Lanxess Deutschland Gmbh Katalysator-Systeme und deren Verwendung für Metathese-Reaktionen
FR2934178B1 (fr) 2008-07-25 2010-09-10 Rhodia Operations Compositions catalytiques pour la metathese de corps gras insatures avec des olefines et procedes de metathese les mettant en oeuvre
EP2157076A1 (fr) 2008-08-21 2010-02-24 Cognis IP Management GmbH Procédé de fabrication de diesters d'acides alpha, oméga dicarboxyliques non saturés

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4654462A (en) * 1985-02-12 1987-03-31 Societe Nationale Elf Aquitaine Metathesis of olefins with a catalyst based upon a tungsten complex
WO2012143067A1 (fr) * 2011-04-20 2012-10-26 Cognis Ip Management Gmbh Procédé de préparation de composés insaturés

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BARGIGGIA F C ET AL: "Cross-metathesis assisted by microwave irradiation", THE JOURNAL OF ORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY, US, vol. 70, 1 January 2005 (2005-01-01), pages 9636 - 9639, XP002466936, ISSN: 0022-3263, DOI: 10.1021/JO0514624 *
CLAVIER H ET AL: "TOWARDS LONG-LIVING METATHESIS CATALYSTS BY TUNING THE N-HETEROCYCLIC CARBENE (NHC) LIGAND ON TRIFLUOROACETAMIDE-ACTIVATED BOOMERANG RU COMPLEXES", EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, WILEY - V C H VERLAG GMBH & CO. KGAA, DE, vol. 2009, no. 25, 1 September 2009 (2009-09-01), pages 4254 - 4265, XP003035086, ISSN: 1434-193X, DOI: 10.1002/EJOC.200900407 *
SEBASTIEN MONFETTE ET AL: "Equilibrium Ring-Closing Metathesis", CHEMICAL REVIEWS, vol. 109, no. 8, 12 August 2009 (2009-08-12), US, pages 3783 - 3816, XP055388545, ISSN: 0009-2665, DOI: 10.1021/cr800541y *

Also Published As

Publication number Publication date
EP2827985B1 (fr) 2018-10-24
WO2013140145A1 (fr) 2013-09-26
EP2827985A1 (fr) 2015-01-28
US20150018574A1 (en) 2015-01-15
GB201204715D0 (en) 2012-05-02
WO2013140144A1 (fr) 2013-09-26
EP2827986A1 (fr) 2015-01-28
US20150045568A1 (en) 2015-02-12
US9816051B2 (en) 2017-11-14
US9604903B2 (en) 2017-03-28

Similar Documents

Publication Publication Date Title
EP2827986B1 (fr) Métathèse d'oléfines avec des complexes catalytiques à base de ruthénium
US20100022789A1 (en) Catalytic compositions for the metathesis of unsaturated fatty bodies with olefins and metathesis methods using catalytic compositions
EP1673328B1 (fr) Procede ameliore de synthese d'alcools insatures
US8604227B2 (en) Process for preparing linear alpha,omega-dicarboxylic diesters
FR3023183A1 (fr) Composition catalytique et procede de dimerisation selective de l'ethylene en butene-1
US10723672B2 (en) Normal alpha olefin synthesis using dehydroformylation or dehydroxymethylation
JPS593972B2 (ja) メタノ−ルからエタノ−ルを製造するための改良同族体化法
US10519088B2 (en) Methods of making functionalized internal olefins and uses thereof
EP3904362A1 (fr) Réactions en présence de complexes de ruthénium
Stewart et al. Reusable Mg–Al hydrotalcites for the catalytic synthesis of diglycerol dicarbonate from diglycerol and dimethyl carbonate
EP3015446B1 (fr) Procédé de production d'alcool allylique et alcool allylique ainsi produit
EP2064166A1 (fr) Procédé de fabrication d'oléfines
TWI452034B (zh) 從２－乙基己醇出發製造異壬酸乙烯酯之製法及其製品
Lazzari et al. Solvent-free catalytic isomerization of perfluoroalkyl allyl ethers
Malacea et al. Alkene metathesis and renewable materials: selective transformations of plant oils
Adilina et al. Recyclable Pd-incorporated perovskite-titanate catalysts synthesized in molten salts for the liquid-phase oxidation of alcohols with molecular oxygen
JP6027437B2 (ja) オレフィンの製造法
US11498889B1 (en) Selective 1-hexene/1-octene production with 1-decene
Bruneau et al. Olefin metathesis in green organic solvents and without solvent
US20150284313A1 (en) Reactions in the presence of ruthenium complexes
Tembe et al. Catalytic tail-to-tail dimerization of methyl acrylate using bis (triphenylphosphine) tricarbonyl ruthenium (0)
WO2017013062A2 (fr) Éthénolyse catalytique d'oléfines insaturées internes éventuellement fonctionnalisées
JP2014129271A (ja) オレフィンの製造方法
FR2525224A1 (fr) Nouveaux complexes de metaux de transition coordones avec un acide de lewis, procede de preparation de ces complexes, utilisation de ces complexes en tant que catalyseurs dans la reaction de metathese des olefines

Legal Events

Date Code Title Description
TPAC Observations filed by third parties

Free format text: ORIGINAL CODE: EPIDOSNTIPA

TPAA Information related to observations by third parties modified

Free format text: ORIGINAL CODE: EPIDOSCTIPA

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140820

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20160314

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C07C 67/475 20060101ALI20180530BHEP

Ipc: B01J 31/22 20060101ALI20180530BHEP

Ipc: C07C 1/213 20060101ALI20180530BHEP

Ipc: C07C 6/02 20060101ALI20180530BHEP

Ipc: B01J 31/14 20060101ALI20180530BHEP

Ipc: B01J 31/12 20060101AFI20180530BHEP

Ipc: C07C 6/04 20060101ALI20180530BHEP

INTG Intention to grant announced

Effective date: 20180627

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1056054

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181115

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602013045515

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1056054

Country of ref document: AT

Kind code of ref document: T

Effective date: 20181024

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190124

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190124

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190224

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190224

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20190125

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602013045515

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20190725

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190318

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20190331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190318

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190331

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20190318

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20130318

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20181024

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230324

Year of fee payment: 11

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230322

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20240320

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240320

Year of fee payment: 12

Ref country code: GB

Payment date: 20240320

Year of fee payment: 12